JP2007165178A - Manufacturing method of cathode for field emission lamp - Google Patents

Manufacturing method of cathode for field emission lamp Download PDF

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JP2007165178A
JP2007165178A JP2005361789A JP2005361789A JP2007165178A JP 2007165178 A JP2007165178 A JP 2007165178A JP 2005361789 A JP2005361789 A JP 2005361789A JP 2005361789 A JP2005361789 A JP 2005361789A JP 2007165178 A JP2007165178 A JP 2007165178A
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cylindrical body
plasma
wire
cathode
field emission
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JP4827515B2 (en
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Minami Ko
南 江
Hirooki O
宏興 王
Hoki Haba
方紀 羽場
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Dialight Japan Co Ltd
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<P>PROBLEM TO BE SOLVED: To provide a new manufacturing method of wire-shaped cathode for field emission lamp. <P>SOLUTION: The manufacturing method uses a plasma generating device having a vacuum chamber 12 and a metallic cylindrical body 14 arranged in the vacuum chamber 12, introducing plasma generating gas in the cylindrical body 14, and generating a plasma in an internal space of the cylindrical body 14 by impressing plasma generating voltage on the cylindrical body; and comprises a first step arranging a wire 16 made of carbon in the cylindrical body 14; a second step forming a metallic film on a surface of a wire 16 by sputtering the cylindrical body by generating plasma for sputtering in the cylindrical body 14; a third step turning the metallic film into metallic fine particles by conducting current and heating the wire 16; and a fourth step generating needle-shaped carbon film by generating a plasma for etching in the cylindrical body 14, and etching the surface of the wire with the metallic fine particles as masks. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

本発明は、電界放射型ランプ用陰極の製造方法に関する。電界放射型ランプは、管タイプ、フラットタイプ、等の種々のタイプのランプが含まれるものであり、ランプの大小、形状を問わない。   The present invention relates to a method for manufacturing a cathode for a field emission lamp. The field emission lamp includes various types of lamps such as a tube type and a flat type, and the size and shape of the lamp are not limited.

電界放射型ランプにおいて、ランプ管内面に蛍光体付きの陽極を形成し、この陽極に電界電子放出源として陰極を対向配置し、陽陰極間に電界を印加して陰極から電子を放出（電界放射）させ、放出した電子を蛍光体に電子衝突させて蛍光体を励起発光させるようになっている。そして、このワイヤ状陰極には導体ワイヤの表面に電子放出用の炭素膜が成膜されており、この炭素膜への電界集中により電子放出が行われるようになっている。   In a field emission lamp, an anode with a phosphor is formed on the inner surface of a lamp tube, a cathode is disposed opposite to the anode as a field electron emission source, and an electric field is applied between the cathode and cathode to emit electrons from the cathode (field emission). And the emitted electrons are caused to collide with the phosphor to cause the phosphor to excite and emit light. In this wire-like cathode, a carbon film for electron emission is formed on the surface of the conductor wire, and electron emission is performed by electric field concentration on the carbon film.

以下、電界放射は、真空に放出される電流密度を記述するファウラノルドハイム（Ｆｏｗｌｅｒ−Ｎｏｒｄｈｅｉｍ）の式で表すことができることが知られている。この式は、
Ｉ＝ｓＡＦ2／φｅｘｐ（−Ｂ3/2／Ｆ）
Ｆ＝βＶ
で与えられる。 In the following, it is known that field emission can be represented by the Fowler-Nordheim equation describing the current density emitted into the vacuum. This formula is
I = sAF 2 / φexp (−B 3/2 / F)
F = βV
Given in.

ただし、Ｉは電界放射電流、ｓは電界放射面積、Ａは定数、Ｆは電界強度、φは仕事関数、Ｂは定数、βは電界集中係数、Ｖは印加電圧である。   Where I is a field emission current, s is a field emission area, A is a constant, F is an electric field strength, φ is a work function, B is a constant, β is an electric field concentration factor, and V is an applied voltage.

電界集中係数βは、印加電圧Ｖを、先端部分の形状や素子の幾何学的形状により電界強度Ｆ（Ｖ／ｃｍ）を変換する係数である。電界放射電流Ｉは、仕事関数φが小さい材料ほど、また、電界集中係数βが大きいほど、強くなり、電界放射電流Ｉが増大する。電子は仕事関数φであるポテンシャル障壁により固体中に閉じ込められている。この固体表面に電界が強く集中し、ポテンシャル障壁が１ｎｍ以下程度にまで薄くなると、電子はその波動性によるトンネリング現象により固体から真空に放射される確率が急激に増大する。このように、電界集中により電子が真空に放射される現象を電界放射（電界電子放出）という。電界放射電流Ｉは、ポテンシャル障壁に衝突する電子の入射密度と、ポテンシャル障壁をトンネリングする確率との積を全エネルギー領域で積分することにより求めることができ、ファウラノルドハイムの式は、そのことを上記式で表したものである。このような電界放射を行う炭素膜として例えば、特許文献１ないし３等で、高アスペクト比のカーボンナノチューブが多数開発されてきている。   The electric field concentration coefficient β is a coefficient for converting the applied voltage V into electric field strength F (V / cm) according to the shape of the tip portion or the geometric shape of the element. The field emission current I becomes stronger as the work function φ is smaller and the field concentration factor β is larger, and the field emission current I increases. Electrons are confined in the solid by a potential barrier having a work function φ. When the electric field is strongly concentrated on the surface of the solid and the potential barrier is thinned to about 1 nm or less, the probability of electrons being emitted from the solid to the vacuum rapidly increases due to the tunneling phenomenon due to the wave nature. A phenomenon in which electrons are radiated to a vacuum due to electric field concentration is called field emission (field electron emission). The field emission current I can be obtained by integrating the product of the incident density of electrons colliding with the potential barrier and the probability of tunneling the potential barrier in the entire energy region, and the Fowler-Nordheim equation expresses that It is expressed by the above formula. For example, Patent Documents 1 to 3 and the like have developed many carbon nanotubes having a high aspect ratio as carbon films that perform such field emission.

このカーボンナノチューブは、針状に炭素膜を化学的気相蒸着（ＣＶＤ）等により成膜したものであり、極めて細長く、その先端部分の曲率半径ｒが小さくなって電界集中係数βが大きくなり、電界放射特性に優れたものとなる。   This carbon nanotube is a needle-like carbon film formed by chemical vapor deposition (CVD) or the like, which is very long and thin, the radius of curvature r at the tip thereof is reduced, and the electric field concentration coefficient β is increased. Excellent field emission characteristics.

しかしながら、カーボンナノチューブの場合、印加電圧を増大させて電界放射電流Ｉを増大させていくに際しては、或る印加電圧を超えると、それ以上は、電界放射電流Ｉが増大しなくなって飽和してしまう、という大きな課題がある。そのため、カーボンナノチューブを電子放出源として、各種のデバイス、装置等に用いる場合、例えば、電界放射型ランプに用いる場合、印加電圧の調整でその発光輝度を調整する場合、その調整範囲が極めて制約されたものとなる。また、カーボンナノチューブでは上記課題以外にも、先端高さが揃いにくくばらつきやすい、先端がゆらぎやすい、基板上に機械的に支持しにくいから安定性にかける、カーボンナノチューブに電流を流し込むための基板との電気的コンタクトがとりにくい、カーボンナノチューブが多数密集すると、電界集中が起こりにくく、電子放出特性が容易に損なわれてしまうこと、等の多数の課題がある。   However, in the case of carbon nanotubes, when the applied voltage is increased to increase the field emission current I, when the applied voltage exceeds a certain applied voltage, the field emission current I does not increase any more and is saturated. There is a big problem. Therefore, when using carbon nanotubes as an electron emission source in various devices, apparatuses, etc., for example, in a field emission lamp, when adjusting the emission luminance by adjusting the applied voltage, the adjustment range is extremely limited. It will be. In addition to the above-mentioned problems, the tip height of the carbon nanotube is difficult to align and easily vary, the tip is likely to fluctuate, and it is difficult to mechanically support the substrate. There are a number of problems such as the difficulty of making electrical contact, and the concentration of a large number of carbon nanotubes makes it difficult for electric field concentration to occur and the electron emission characteristics are easily impaired.

そこで、本出願人は、特願２００５−２４４４０９（平成１７年８月２５日出願）で上記課題を解決した発明について出願（発明の名称「炭素膜、電子放出源および電界放射型照明ランプ」）（先行出願）したのである。この先行出願においては、ファウラノルドハイムの式における電界集中係数βが、任意の位置での先端までの高さをｈ、半径をｒとして、ｈ／ｒの式で表され、かつ、その半径が任意の位置から先端に向かうにつれて小さくなる形状を備えた針状炭素膜である。   Therefore, the present applicant has filed an application for the invention that has solved the above problems in Japanese Patent Application No. 2005-244409 (filed on August 25, 2005) (title of the invention "carbon film, electron emission source and field emission illumination lamp"). (Prior application). In this prior application, the electric field concentration factor β in the Fowler-Nordheim equation is represented by the equation h / r, where h is the height to the tip at an arbitrary position and r is the radius, and the radius is It is a needle-like carbon film having a shape that decreases from an arbitrary position toward the tip.

ところで、電界放射型ランプには、陽極に対して陰極をワイヤ状に対向配置し、このワイヤ状に延びた陰極表面の全体から電子を放出させるものがある。このようなワイヤの表面に上記針状炭素膜を成膜して陰極を製造するに際して、本出願人は、安価に製造できること、高い生産性で量産することができること、に加えて、電界放射型ランプの大型大面積化に対応してより長尺なワイヤ状の陰極を製造することができる製造技術について検討した。
特開２００５−３１４２０６ 特開２００５−３１４２０４ 特開２００５−２７２２７１ By the way, in some field emission lamps, a cathode is disposed opposite to an anode in a wire shape, and electrons are emitted from the entire surface of the cathode extending in the wire shape. In manufacturing the cathode by forming the acicular carbon film on the surface of such a wire, the present applicant can manufacture it at low cost, mass production with high productivity, field emission type A manufacturing technique capable of manufacturing a longer wire-like cathode in response to an increase in the area of a large lamp was investigated.
JP-A-2005-314206 JP-A-2005-314204 JP-A-2005-272271

本発明は、電界放射型ランプ用陰極にワイヤ表面に針状炭素膜を安価で高歩留まりで成膜可能として、当該陰極を低いコストで量産することができ、そのうえ、長尺ないしは超長尺なワイヤ状陰極をも容易に製造できる新規な製造方法を提供することを目的としている。   The present invention makes it possible to form a needle-like carbon film on a wire surface on a wire emission field cathode at a low cost with a high yield, and to mass-produce the cathode at a low cost. It aims at providing the novel manufacturing method which can manufacture a wire-shaped cathode easily.

（１）本発明第１に係る電界放射型ランプ用陰極の製造方法は、真空チャンバと、真空チャンバ内に配置される金属製の筒状体とを備え、上記筒状体にプラズマ発生用ガスを導入しかつプラズマ発生用電圧を印加して筒状体の内部空間にプラズマを発生させるプラズマ発生装置を用いて、筒状体に炭素からなるワイヤを配置する第１ステップと、筒状体内にスパッタ用のプラズマを発生させて筒状体をスパッタリングしてワイヤ表面に金属膜を成膜する第２ステップと、ワイヤに通電加熱して金属膜を多数の金属微粒子にする第３ステップと、筒状体内に高周波のエッチング用プラズマを発生させて金属微粒子をマスクにしてワイヤ表面をエッチングして針状炭素膜を生成する第４ステップと、を含むことを特徴とする。   (1) A method of manufacturing a cathode for a field emission lamp according to the first aspect of the present invention includes a vacuum chamber and a metal cylinder disposed in the vacuum chamber, and the plasma generating gas is provided in the cylinder. And applying a plasma generation voltage to generate plasma in the inner space of the cylindrical body, using a plasma generator to place a wire made of carbon in the cylindrical body, and in the cylindrical body A second step of generating a plasma for sputtering to sputter a cylindrical body to form a metal film on the surface of the wire; a third step of energizing and heating the wire to convert the metal film into a large number of metal fine particles; And a fourth step of generating a needle-like carbon film by generating a high-frequency etching plasma in the rod and etching the wire surface using the metal fine particles as a mask.

上記金属微粒子は、好ましくは直径１〜１００ｎｍ程度である。金属微粒子の生成間隔は、針状炭素膜の電界集中作用を確保することができる程度であることが好ましい。   The metal fine particles preferably have a diameter of about 1 to 100 nm. It is preferable that the generation interval of the metal fine particles is such that the electric field concentration action of the acicular carbon film can be secured.

針状炭素膜は、好ましくは直径がｎｍオーダーで、高さがμｍオーダーである。   The acicular carbon film preferably has a diameter on the order of nm and a height on the order of μm.

針状炭素膜は、先端に向かうほど細くなることが好ましい。   The acicular carbon film is preferably thinner toward the tip.

針状炭素膜は、ファウラノルドハイムの式における電界集中係数βが、任意の位置での先端までの高さをｈ、半径をｒとして、ｈ／ｒの式で表される形状であることが好ましい。   The acicular carbon film has a shape represented by the equation h / r, where the electric field concentration factor β in the Fowler-Nordheim equation is h, where r is the height to the tip at an arbitrary position. preferable.

プラズマ発生用電圧は、高周波であることが好ましい。   The plasma generating voltage is preferably a high frequency.

本発明第１の製造方法においては、針状炭素膜を製造するために、第１ステップでプラズマスパッタ、第２ステップで熱処理、第３ステップでプラズマエッチングという３ステップを備えるが、この３ステップを同一のプラズマ発生装置で実施することができるものであり、安価で量産性に優れかつ長尺なワイヤ状陰極を製造することができる。   In the first manufacturing method of the present invention, in order to manufacture the acicular carbon film, the first step includes plasma sputtering in the first step, heat treatment in the second step, and plasma etching in the third step. It can be implemented with the same plasma generator, and can produce a long, wire-like cathode that is inexpensive, excellent in mass productivity.

すなわち、従来の製造方法により、針状炭素膜を備えた電界放射型ランプ用陰極を製造する場合、プラズマスパッタ装置と、熱処理装置と、プラズマエッチング装置とが必要であり、極めて高価となる上に、量産性も落ちるとともに、長尺なワイヤ状陰極を製造することが困難である。   That is, when a field emission lamp cathode having a needle-like carbon film is manufactured by a conventional manufacturing method, a plasma sputtering device, a heat treatment device, and a plasma etching device are required, which is extremely expensive. Further, mass productivity is lowered, and it is difficult to manufacture a long wire cathode.

これに対して、本発明第１では、１台のプラズマ発生装置により、上記第１ないし第３ステップを実施することができるので、安価に済むとともに、量産性も向上する。また、筒状体を用いるので、長尺なワイヤ状陰極を製造する場合では、その長尺寸法に合わせて筒状体を延長して長尺なワイヤ状陰極を製造することができる。   On the other hand, according to the first aspect of the present invention, the first to third steps can be performed by one plasma generator, so that the cost is low and the mass productivity is improved. Moreover, since a cylindrical body is used, when manufacturing a long wire-like cathode, a cylindrical body can be extended according to the long dimension, and a long wire-like cathode can be manufactured.

（２）本発明第２に係る電界放射型ランプ用陰極の製造方法は、真空チャンバと、真空チャンバ内に配置される金属製の筒状体とを備え、上記筒状体にプラズマ発生用ガスを導入しかつプラズマ発生用電圧を印加して筒状体の内部空間にプラズマを発生させるプラズマ発生装置を用いて、筒状体に金属からなるワイヤを配置する第１ステップと、筒状体内に炭素膜成膜用のプラズマを発生させてワイヤ表面に炭素膜を成膜する第２ステップと、筒状体内にスパッタ用のプラズマを発生させて筒状体をスパッタして炭素膜表面に金属膜を成膜する第３ステップと、ワイヤに通電加熱して金属膜を多数の金属微粒子にする第４ステップと、筒状体内にエッチング用プラズマを発生させて金属微粒子をマスクにしてワイヤ表面をエッチングして針状炭素膜を生成する第５ステップと、を含むことを特徴とする。   (2) A method of manufacturing a cathode for a field emission lamp according to the second aspect of the present invention includes a vacuum chamber and a metal cylindrical body disposed in the vacuum chamber, and the plasma generating gas is provided in the cylindrical body. And applying a plasma generation voltage to generate plasma in the internal space of the cylindrical body, and using the plasma generator to place a wire made of metal on the cylindrical body, and in the cylindrical body A second step of generating a carbon film on the wire surface by generating a plasma for forming a carbon film, and a sputtering film is generated in the cylindrical body to sputter the cylindrical body to form a metal film on the surface of the carbon film. The third step of forming a film, the fourth step of energizing and heating the wire to turn the metal film into a large number of metal fine particles, and generating the etching plasma in the cylindrical body to etch the wire surface using the metal fine particles as a mask Needle shape Characterized in that it comprises a fifth step of generating Motomaku, the.

この製造方法では上記（１）の作用効果に加えてワイヤが金属であるので機械的な強度が高い、針状炭素膜を備えたワイヤ状陰極を製造することができる。   In this manufacturing method, in addition to the effect (1), a wire-like cathode having a needle-like carbon film having high mechanical strength can be produced because the wire is a metal.

筒状体の形状は何等限定されないが、例えばコイル状、円筒状、柵状、籠状、あるいは対向した２つ一対の筒体等を例示することができる。   Although the shape of a cylindrical body is not limited at all, For example, a coil shape, a cylindrical shape, a fence shape, a bowl shape, or two pairs of cylindrical bodies facing each other can be exemplified.

筒状体の周壁をコイル状や網目状とした場合、その螺旋径、螺旋ピッチを調整して筒状体の形状を調整することにより、所望密度のプラズマを発生させることができる。また、筒状体の周壁をコイル状や網目状とした場合、弾性を持たせて、プラズマ発生時に筒状体が熱膨張した場合等においては、そのコイル状や網目状の形状により熱膨張を吸収することができ、熱膨張による応力を緩和することができ、筒状体の寿命を伸ばすことができるようになる。筒状体の周壁を複数の電線により筒状体の筒軸方向に平行に円周方向等間隔に配置した柵状や籠状にした場合、筒状体と基板との間にプラズマを高効率で発生させることができるようになる。   When the peripheral wall of the cylindrical body is coiled or mesh-shaped, plasma having a desired density can be generated by adjusting the shape of the cylindrical body by adjusting the helical diameter and the helical pitch. In addition, when the cylindrical body has a coiled or mesh-like peripheral wall, it has elasticity, and when the cylindrical body thermally expands during plasma generation, the thermal expansion is caused by the coiled or mesh-like shape. It can be absorbed, stress due to thermal expansion can be relieved, and the lifetime of the cylindrical body can be extended. When the peripheral wall of the cylindrical body is made into a fence shape or a bowl shape that is arranged at equal intervals in the circumferential direction parallel to the cylindrical axis direction of the cylindrical body with a plurality of electric wires, high efficiency of plasma is generated between the cylindrical body and the substrate Can be generated at.

本発明により製造した針状炭素膜を備えたワイヤは電界放射型ランプのワイヤ状陰極（冷陰極電子源）とし、このワイヤ状陰極と対向する陽極との間の電界印加により電子放出させ、この電子を蛍光体に衝突させて該蛍光体を励起発光する電界放射型ランプに適用することができる。   A wire having a needle-like carbon film manufactured according to the present invention is used as a wire-like cathode (cold cathode electron source) of a field emission lamp, and electrons are emitted by applying an electric field between the wire-like cathode and an anode facing the cathode. The present invention can be applied to a field emission lamp that emits light by exciting electrons by colliding with the phosphor.

本発明によれば、表面に針状炭素膜を備えたワイヤ状陰極を安価にかつ高い量産性で製造することができることに加えて長尺なワイヤ状陰極をも製造することができる。   According to the present invention, in addition to being able to produce a wire-like cathode having a needle-like carbon film on its surface at low cost and with high productivity, it is also possible to produce a long wire-like cathode.

以下、添付した図面を参照して、本発明の実施の形態に係る電界放射型ランプ用陰極の製造方法を説明する。   Hereinafter, a method for manufacturing a cathode for a field emission lamp according to an embodiment of the present invention will be described with reference to the accompanying drawings.

図１は同製造方法の実施に用いるプラズマ発生装置の構成を模式的に示す図である。このプラズマ発生装置１０は、真空チャンバ１２を備える。真空チャンバ１２はガス導入口１２ａとガス排出口１２ｂとを備える。真空チャンバ１２の内部には金属材例えばＳＵＳ等の鉄材からなる断面円形の筒状体１４が配置されている。筒状体１４は、コイル構造になっている。筒状体１４の内部空間には炭素からなるワイヤ１６が配置されている。筒状体１４は一方向にストレートに延びており、筒状体１４の内部空間は一方向に長く延びる円筒形のプラズマ発生用の空間をなしている。ワイヤ１６はこの内部空間に配置されて細長に延びた構造になっている。筒状体１６の内周面とワイヤ１６の外周面とはその延設方向に所要の空間を隔てて相対向している。筒状体１４の両端はプラズマ発生用電圧源としての高周波電源１８に接続されている。ワイヤ１６の両端は通電加熱用電源としての交流電源２０が接続され、かつ、その一端側には直流電源２２の負極に接続されて直流負バイアスが印加されている。   FIG. 1 is a diagram schematically showing a configuration of a plasma generator used for carrying out the manufacturing method. The plasma generator 10 includes a vacuum chamber 12. The vacuum chamber 12 includes a gas inlet 12a and a gas outlet 12b. Inside the vacuum chamber 12, a cylindrical body 14 having a circular cross section made of a metal material such as an iron material such as SUS is disposed. The cylindrical body 14 has a coil structure. A wire 16 made of carbon is disposed in the internal space of the cylindrical body 14. The cylindrical body 14 extends straight in one direction, and the internal space of the cylindrical body 14 forms a cylindrical plasma generation space extending long in one direction. The wire 16 is disposed in this internal space and has a structure extending in an elongated shape. The inner peripheral surface of the cylindrical body 16 and the outer peripheral surface of the wire 16 are opposed to each other with a required space in the extending direction. Both ends of the cylindrical body 14 are connected to a high-frequency power source 18 as a plasma generating voltage source. Both ends of the wire 16 are connected to an AC power source 20 as a power source for energization heating, and one end thereof is connected to the negative electrode of the DC power source 22 and applied with a DC negative bias.

以上の構成を備えたプラズマ発生装置１０を用いた実施の形態１の針状炭素膜の製造方法を図２を参照して説明する。   A method of manufacturing the acicular carbon film of the first embodiment using the plasma generator 10 having the above configuration will be described with reference to FIG.

まず、真空チャンバ１２のガス導入口１２ａからスパッタ用ガスの一例としてアルゴンガスを導入する。筒状体１４の両端にプラズマ発生用電圧源である高周波電源１８から高周波電圧を印加する。図２（ａ）の断面を有するワイヤ１６に直流電源２２の直流負バイアスを印加する。   First, argon gas is introduced as an example of a sputtering gas from the gas inlet 12 a of the vacuum chamber 12. A high frequency voltage is applied to both ends of the cylindrical body 14 from a high frequency power source 18 which is a plasma generating voltage source. A DC negative bias of the DC power supply 22 is applied to the wire 16 having the cross section of FIG.

また、ワイヤ１６の両端に交流電源の交流電圧を印加する。これによって、スパッタ用のアルゴンプラズマが発生し、このアルゴンプラズマ中に存在するアルゴンイオンにより筒状体１４がターゲット材としてスパッタされ、ワイヤ１６表面に金属膜（鉄膜）２４が成膜される。このときのワイヤ１６の一部断面を図２（ｂ）に示す。なお、金属膜２４はμｍオーダー厚の薄膜であり、ワイヤ１６は数ｍｍ径であるが、図２（ａ）ないし図２（ｅ）は理解のため、寸法関係を無視し誇張して示している。   Further, an AC voltage of an AC power source is applied to both ends of the wire 16. Thereby, argon plasma for sputtering is generated, and the cylindrical body 14 is sputtered as a target material by argon ions existing in the argon plasma, and a metal film (iron film) 24 is formed on the surface of the wire 16. A partial cross section of the wire 16 at this time is shown in FIG. The metal film 24 is a thin film having a thickness on the order of μm, and the wire 16 has a diameter of several millimeters. However, for the sake of understanding, FIG. 2A to FIG. Yes.

次に、ワイヤ１６は交流電圧の印加で加熱されていて高温であるので、成膜された金属膜２４はこの加熱により多数の金属微粒子２６になる。図２（ｃ）にその様子を示す。ワイヤ１６表面の金属膜２４が微粒子化することにより、ワイヤ１６の表面において、金属微粒子２６が存在しない表面が露出する。   Next, since the wire 16 is heated by application of an alternating voltage and has a high temperature, the formed metal film 24 becomes a large number of metal fine particles 26 by this heating. This is shown in FIG. By forming the metal film 24 on the surface of the wire 16 into fine particles, the surface of the wire 16 where the metal fine particles 26 do not exist is exposed.

次に、真空チャンバ１２中にアルミ材からなる筒状体１４を配置し、その筒状体１４内に図２（ｃ）に示すワイヤ１６を配置する。そして、真空チャンバ１２にエッチング用のガスの一例である酸素ガスを導入するとともに、筒状体１４の両端に高周波電源１８の高周波電圧を印加し、ワイヤ１６に直流電源２２の直流負バイアスを印加し、ワイヤ１６の両端に交流電源の交流電圧を印加する。これによって、筒状体１４内にエッチング用のプラズマである酸素プラズマが発生する。このとき、筒状体１４表面は薄く酸化されている。ワイヤ１６は、その表面に金属微粒子２６が付着している部分はエッチングされず、金属微粒子２６が付着せずワイヤ１６の表面が露出している部分は図２（ｄ）で示すようにエッチングされて、金属微粒子２６の下方に針状炭素膜２８が生成される。金属微粒子２６は針状炭素膜２８上に存在してもよいが、適宜、酸処理により図２（ｅ）で示すように除去してワイヤ１６表面に針状炭素膜のみを作製することができる。   Next, a cylindrical body 14 made of an aluminum material is arranged in the vacuum chamber 12, and a wire 16 shown in FIG. 2C is arranged in the cylindrical body 14. Then, oxygen gas, which is an example of an etching gas, is introduced into the vacuum chamber 12, a high-frequency voltage of the high-frequency power source 18 is applied to both ends of the cylindrical body 14, and a DC negative bias of the DC power source 22 is applied to the wire 16. Then, an AC voltage of an AC power source is applied to both ends of the wire 16. As a result, oxygen plasma, which is plasma for etching, is generated in the cylindrical body 14. At this time, the surface of the cylindrical body 14 is thinly oxidized. The portion of the wire 16 where the metal fine particles 26 adhere to the surface is not etched, and the portion where the metal fine particles 26 do not adhere and the surface of the wire 16 is exposed is etched as shown in FIG. Thus, a needle-like carbon film 28 is generated below the metal fine particles 26. The metal fine particles 26 may be present on the acicular carbon film 28, but can be appropriately removed by acid treatment as shown in FIG. 2 (e) to produce only the acicular carbon film on the surface of the wire 16. .

次に、図３を参照して実施の形態２の製造方法を説明する。   Next, the manufacturing method of Embodiment 2 is demonstrated with reference to FIG.

実施の形態２においては、筒状体１４内に金属材例えば鉄材からなるワイヤ１６を配置する。図３（ａ）にこのワイヤ１６の一部断面を示す。この配置の完了後に、筒状体１４の両端に高周波電源１８の高周波電圧を印加し、ワイヤ１６の両端に交流電源２０の交流電圧を印加し、ワイヤ１６に直流電源２２の直流負バイアスを印加するとともに、真空チャンバ１２のガス導入口１２ａから炭素膜成膜用のガスの一例である炭化水素ガスと水素ガスとを導入する。これによって、筒状体１４内に水素プラズマが発生し、ワイヤ１６表面に炭素膜３０が成膜される。この炭素膜３０の成膜状態を図３（ｂ）に示す。なお、炭素膜３０はμｍオーダー厚の薄膜であり、ワイヤ１６は数ｍｍ径であるが、図３（ａ）ないし図３（ｆ）は理解のため寸法関係を無視して誇張して示している。   In the second embodiment, a wire 16 made of a metal material such as an iron material is disposed in the cylindrical body 14. FIG. 3A shows a partial cross section of the wire 16. After this arrangement is completed, the high frequency voltage of the high frequency power supply 18 is applied to both ends of the cylindrical body 14, the AC voltage of the AC power supply 20 is applied to both ends of the wire 16, and the DC negative bias of the DC power supply 22 is applied to the wire 16. At the same time, a hydrocarbon gas and a hydrogen gas, which are examples of a carbon film forming gas, are introduced from the gas inlet 12 a of the vacuum chamber 12. As a result, hydrogen plasma is generated in the cylindrical body 14, and the carbon film 30 is formed on the surface of the wire 16. The film formation state of the carbon film 30 is shown in FIG. The carbon film 30 is a thin film having a thickness on the order of μm, and the wire 16 has a diameter of several millimeters. However, FIG. 3A to FIG. Yes.

次に、炭素膜３０表面にプラズマスパッタリングにより金属膜３２を成膜する。これには、真空チャンバ１２のガス導入口１２ａからアルゴンガスを導入する。筒状体１４の両端に高周波電源１８の高周波電圧を印加する。ワイヤ１６に直流電源２２の直流負バイアスを印加する。また、ワイヤ１６の両端に交流電源２０の交流電圧を印加する。これによって、スパッタ用のアルゴンプラズマが発生し、このアルゴンプラズマ中に存在するアルゴンイオンにより筒状体１４がターゲット材としてスパッタされ、炭素膜３０表面に金属膜（鉄膜）３２が成膜される。図３（ｃ）にそのときのワイヤ１６の一部断面を示す。   Next, a metal film 32 is formed on the surface of the carbon film 30 by plasma sputtering. For this purpose, argon gas is introduced from the gas inlet 12 a of the vacuum chamber 12. A high frequency voltage of a high frequency power source 18 is applied to both ends of the cylindrical body 14. A DC negative bias of the DC power supply 22 is applied to the wire 16. Further, an AC voltage of the AC power supply 20 is applied to both ends of the wire 16. As a result, sputtering argon plasma is generated, and the cylindrical body 14 is sputtered as a target material by argon ions existing in the argon plasma, and a metal film (iron film) 32 is formed on the surface of the carbon film 30. . FIG. 3C shows a partial cross section of the wire 16 at that time.

次に、ワイヤ１６は交流電圧の印加で加熱されていて高温であるので、成膜された金属膜３２はこの加熱により多数の金属微粒子３４になる。図３（ｄ）にその様子を示す。炭素膜３０表面の金属膜３２が微粒子化することにより、炭素膜３０表面のうち金属微粒子３４が存在しない表面が露出する。   Next, since the wire 16 is heated by application of an alternating voltage and has a high temperature, the formed metal film 32 becomes a large number of metal fine particles 34 by this heating. This is shown in FIG. By forming the metal film 32 on the surface of the carbon film 30 into fine particles, the surface of the carbon film 30 on which the metal fine particles 34 do not exist is exposed.

次に、真空チャンバ１２中にアルミ材からなる筒状体１４を配置し、その筒状体１４内に図３（ｄ）のワイヤ１６を配置する。そして、真空チャンバ１２に酸素ガスを導入するとともに、筒状体１４の両端に高周波電源１８の高周波電圧を印加し、ワイヤ１６に直流電源２２の直流負バイアスを印加し、ワイヤ１６の両端に交流電源２０の交流電圧を印加する。これによって、筒状体１４内にエッチング用の酸素プラズマが発生する。このとき、筒状体１４表面は薄く酸化されている。炭素膜３０の表面に金属微粒子３２が付着している部分はエッチングされず、金属微粒子３２が付着せず表面が露出している炭素膜部分は図３（ｅ）で示すようにエッチングされて、針状炭素膜３６が生成される。金属微粒子３４は針状炭素膜３６上にそのまま存在してもよいが、適宜、酸処理により図３（ｆ）で示すように除去し、ワイヤ１６表面に針状炭素膜３６のみを作製することができる。   Next, a cylindrical body 14 made of an aluminum material is disposed in the vacuum chamber 12, and the wire 16 in FIG. 3D is disposed in the cylindrical body 14. Then, oxygen gas is introduced into the vacuum chamber 12, a high frequency voltage of the high frequency power supply 18 is applied to both ends of the cylindrical body 14, a DC negative bias of the DC power supply 22 is applied to the wire 16, and AC is applied to both ends of the wire 16. An AC voltage from the power source 20 is applied. Thereby, oxygen plasma for etching is generated in the cylindrical body 14. At this time, the surface of the cylindrical body 14 is thinly oxidized. The portion where the metal fine particles 32 are attached to the surface of the carbon film 30 is not etched, and the carbon film portion where the metal fine particles 32 are not attached and the surface is exposed is etched as shown in FIG. The acicular carbon film 36 is generated. The metal fine particles 34 may exist on the acicular carbon film 36 as they are, but are appropriately removed by acid treatment as shown in FIG. 3 (f) to produce only the acicular carbon film 36 on the surface of the wire 16. Can do.

この針状炭素膜２８，３６について図４を参照して説明する。   The acicular carbon films 28 and 36 will be described with reference to FIG.

実施の形態の針状炭素膜２８，３６では、図４（ａ）で示すように、電界集中係数βが、上記ｈ／ｒの式で表され、かつ、基部から先端部分Ｓ１に向けて半径ｒvが小さくなる形状を有するから、図４（ｂ）で示す（実線曲線は実施の形態の針状炭素膜により、二点鎖線曲線はカーボンナノチューブによる）ように、印加電圧Ｖが増大するにつれ先端部分から矢印Ａのように電界放射し、さらに印加電圧Ｖが増大すると、先端部分Ｓ１から遠くなる部分Ｓ２からも矢印Ｂのように電界放射が起こり、さらに印加電圧Ｖが増大すると、先端部分Ｓ１からさらに遠くなる部分Ｓ３からも矢印Ｃのように電界放射が起こる。 In the acicular carbon films 28 and 36 of the embodiment, as shown in FIG. 4A, the electric field concentration coefficient β is expressed by the above equation h / r, and the radius from the base portion toward the tip portion S1. since having a shape r v is small, (the needle-like carbon film of the solid curve the embodiment, the chain line curve two points by the carbon nanotubes) shown in FIG. 4 (b) as such, the applied voltage V is increased When the electric field is radiated from the tip portion as indicated by an arrow A and the applied voltage V is further increased, the electric field is emitted from the portion S2 far from the tip portion S1 as indicated by an arrow B, and when the applied voltage V is further increased, the tip portion Field emission also occurs as indicated by an arrow C from a portion S3 farther from S1.

このようにして実施の形態の針状炭素膜２８，３６では、印加電圧Ｖの増大により、電界放射電流Ｉが従来のように印加電圧ＶがＶ0を超えても、電界放射電流Ｉがカーボンナノチューブのように電流Ｉ0で飽和せず、それ以上に増大することができる炭素膜である。 In this way, in the acicular carbon films 28 and 36 of the embodiment, even when the applied voltage V exceeds V 0 as in the prior art due to the increase of the applied voltage V, the field emitted current I is carbon. It is a carbon film that does not saturate at a current I 0 and can be increased beyond that, like a nanotube.

これによって、実施の形態の針状炭素膜２８，３６は、例えば、電界放射型の照明ランプにおいてその発光輝度を任意の輝度に容易に制御することができるようになる。   Thereby, the acicular carbon films 28 and 36 of the embodiment can easily control the emission luminance to an arbitrary luminance in, for example, a field emission type illumination lamp.

図１は本発明の実施の形態に係る電界放射型ランプ用陰極の製造方法の実施に用いるプラズマ発生装置の構成を示す図である。FIG. 1 is a diagram showing a configuration of a plasma generating apparatus used for carrying out a manufacturing method of a field emission lamp cathode according to an embodiment of the present invention. 図２は実施の形態１の電界放射型ランプ用陰極の製造方法における各工程でのワイヤの断面図である。FIG. 2 is a cross-sectional view of the wire at each step in the method of manufacturing the cathode for the field emission lamp of the first embodiment. 図３は実施の形態２の電界放射型ランプ用陰極の製造方法における各工程でのワイヤの断面図である。FIG. 3 is a cross-sectional view of a wire at each step in the method of manufacturing a cathode for a field emission lamp according to the second embodiment. 図４は本発明の製造に係る電界放射型ランプ用陰極が備える針状炭素膜の特性の説明に供する図である。FIG. 4 is a diagram for explaining the characteristics of the acicular carbon film provided in the field emission lamp cathode according to the production of the present invention.

符号の説明Explanation of symbols

１０ プラズマ発生装置
１２ 真空チャンバ
１４ 筒状体
１６ ワイヤ
１８ 高周波電源
２０ 交流電源
２２ 直流電源
２４ 金属膜
２６ 金属微粒子
２８ 針状炭素膜 DESCRIPTION OF SYMBOLS 10 Plasma generator 12 Vacuum chamber 14 Tubular body 16 Wire 18 High frequency power source 20 AC power source 22 DC power source 24 Metal film 26 Metal fine particle 28 Acicular carbon film

Claims (13)

真空チャンバと、真空チャンバ内に配置される金属製の筒状体とを備え、上記筒状体にプラズマ発生用ガスを導入しかつプラズマ発生用電圧を印加して筒状体の内部空間にプラズマを発生させるプラズマ発生装置を用いて、
筒状体に炭素からなるワイヤを配置する第１ステップと、
筒状体内にスパッタ用プラズマを発生させて筒状体をスパッタリングしてワイヤ表面に金属膜を成膜する第２ステップと、
ワイヤに通電加熱して金属膜を多数の金属微粒子にする第３ステップと、
筒状体内にエッチング用プラズマを発生させ、金属微粒子をマスクにして、ワイヤ表面をエッチングして針状炭素膜を生成する第４ステップと、
を含む、ことを特徴とする電界放射型ランプ用陰極の製造方法。 A vacuum chamber and a metal cylindrical body disposed in the vacuum chamber, and a plasma generating gas is introduced into the cylindrical body and a plasma generating voltage is applied to the inner space of the cylindrical body. Using a plasma generator that generates
A first step of placing a wire made of carbon on the tubular body;
A second step of generating a plasma for sputtering in the cylindrical body to sputter the cylindrical body to form a metal film on the wire surface;
A third step of energizing and heating the wire to convert the metal film into a large number of fine metal particles;
A fourth step of generating etching plasma in the cylindrical body, etching the wire surface using the metal fine particles as a mask, and generating a needle-like carbon film;
A method for producing a cathode for a field emission lamp, comprising: 上記第２ステップにおいて、アルゴンプラズマを用いたスパッタリングである、ことを特徴とする請求項１に記載の電界放射型ランプ用陰極の製造方法。   The method of manufacturing a cathode for a field emission lamp according to claim 1, wherein the second step is sputtering using argon plasma. 上記第３ステップにおいて、酸素プラズマを用いたエッチングである、ことを特徴とする請求項１または２に記載の電界放射型ランプ用陰極の製造方法。   3. The method of manufacturing a cathode for a field emission lamp according to claim 1, wherein the third step is an etching using oxygen plasma. 上記第１ないし第３ステップにおいて、筒状体として鉄材からなる筒状体を用いる、ことを特徴とする請求項３に記載の電界放射型ランプ用陰極の製造方法。   4. The method of manufacturing a cathode for a field emission lamp according to claim 3, wherein a cylindrical body made of an iron material is used as the cylindrical body in the first to third steps. 上記第４ステップにおいて、筒状体としてアルミ材からなる筒状体を用いる、ことを特徴とする請求項３に記載の電界放射型ランプ用陰極の製造方法。   4. The method for manufacturing a cathode for a field emission lamp according to claim 3, wherein in the fourth step, a cylindrical body made of an aluminum material is used as the cylindrical body. 上記第４ステップの後、金属微粒子を酸により除去する第５ステップを含む、ことを特徴とする請求項１ないし５のいずれかに記載の電界放射型ランプ用陰極の製造方法。   6. The method for producing a cathode for a field emission lamp according to claim 1, further comprising a fifth step of removing the metal fine particles with an acid after the fourth step. 真空チャンバと、真空チャンバ内に配置される金属製の筒状体とを備え、上記筒状体にプラズマ発生用ガスを導入しかつプラズマ発生用電圧を印加して筒状体の内部空間にプラズマを発生させるプラズマ発生装置を用いて、
筒状体に金属からなるワイヤを配置する第１ステップと、
筒状体内に炭素膜成膜用のプラズマを発生させてワイヤ表面に炭素膜を成膜する第２ステップと、
筒状体内にスパッタ用のプラズマを発生させて筒状体をスパッタして炭素膜表面に金属膜を成膜する第３ステップと、
ワイヤに通電加熱して金属膜を多数の金属微粒子にする第４ステップと、
筒状体内にエッチング用プラズマを発生させ、金属微粒子をマスクにして、ワイヤ表面をエッチングして針状炭素膜を生成する第５ステップと、
を含むことを特徴とする電界放射型ランプ用陰極の製造方法。 A vacuum chamber and a metal cylindrical body disposed in the vacuum chamber, and a plasma generating gas is introduced into the cylindrical body and a plasma generating voltage is applied to the inner space of the cylindrical body. Using a plasma generator that generates
A first step of disposing a metal wire on the cylindrical body;
A second step of generating a carbon film on the wire surface by generating a plasma for forming a carbon film in the cylindrical body;
A third step of generating a plasma for sputtering in the cylindrical body to sputter the cylindrical body to form a metal film on the surface of the carbon film;
A fourth step of energizing and heating the wire to convert the metal film into a large number of fine metal particles;
A fifth step of generating etching plasma in the cylindrical body, etching the wire surface using the metal fine particles as a mask, and generating a needle-like carbon film;
A method for producing a cathode for a field emission lamp, comprising: 上記第３ステップにおいて、アルゴンプラズマを用いたスパッタリングである、ことを特徴とする請求項７に記載の電界放射型ランプ用陰極の製造方法。   8. The method of manufacturing a cathode for a field emission lamp according to claim 7, wherein the third step is sputtering using argon plasma. 上記第５ステップにおいて、酸素プラズマを用いたエッチングである、ことを特徴とする請求項７または８に記載の電界放射型ランプ用陰極の製造方法。   9. The method of manufacturing a cathode for a field emission lamp according to claim 7, wherein the fifth step is etching using oxygen plasma. 上記第１ないし第４ステップにおいて、筒状体として鉄材からなる筒状体を用いる、ことを特徴とする請求項９に記載の電界放射型ランプ用陰極の製造方法。   The method for manufacturing a cathode for a field emission lamp according to claim 9, wherein a cylindrical body made of an iron material is used as the cylindrical body in the first to fourth steps. 上記第５ステップにおいて、筒状体としてアルミ材からなる筒状体を用いる、ことを特徴とする請求項９に記載の電界放射型ランプ用陰極の製造方法。   The method for manufacturing a cathode for a field emission lamp according to claim 9, wherein in the fifth step, a cylindrical body made of an aluminum material is used as the cylindrical body. 第５ステップの後、金属微粒子を酸により除去する第６ステップを含む、ことを特徴とする請求項７ないし１１のいずれかに記載の電界放射型ランプ用陰極の製造方法。   12. The method of manufacturing a cathode for a field emission lamp according to claim 7, further comprising a sixth step of removing the metal fine particles with an acid after the fifth step. プラズマ発生用電圧が、高周波電圧である、ことを特徴とする請求項１ないし１２のいずれかに記載の電界放射型ランプ用陰極の製造方法。   The method for producing a cathode for a field emission lamp according to any one of claims 1 to 12, wherein the plasma generating voltage is a high-frequency voltage.
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Publication number Priority date Publication date Assignee Title
JP2010198970A (en) * 2009-02-26 2010-09-09 Stanley Electric Co Ltd Method of manufacturing field emission electron source

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JP2000215788A (en) * 1998-11-19 2000-08-04 Nec Corp Carbon material and its manufacture and field emission type cold cathode by using it
JP2002509339A (en) * 1997-12-15 2002-03-26 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー Ion bombarded graphite electron emitter on coated wire
JP2005307352A (en) * 2004-03-25 2005-11-04 Dialight Japan Co Ltd Apparatus for producing carbon film and production method therefor

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Publication number Priority date Publication date Assignee Title
JP2002509339A (en) * 1997-12-15 2002-03-26 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー Ion bombarded graphite electron emitter on coated wire
JP2000215788A (en) * 1998-11-19 2000-08-04 Nec Corp Carbon material and its manufacture and field emission type cold cathode by using it
JP2005307352A (en) * 2004-03-25 2005-11-04 Dialight Japan Co Ltd Apparatus for producing carbon film and production method therefor

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010198970A (en) * 2009-02-26 2010-09-09 Stanley Electric Co Ltd Method of manufacturing field emission electron source

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